Polyethylene glycol esters in fat



Patented Jan. 19, 1954 POLYETHYLENE GLYCOL ESTERS IN FAT Emery I. Valko, Mountain Lakes, N. J., assignor to E. F. Drew & 00., Inc., New York, N. Y., a

corporation of Delaware No Drawing. Application November 16, 1949, Serial No. 127,762

8 Claims. (Cl. 99-123) The present invention is directed to polyethylv ene glycol esters, and more particularly to materials having utility in connection with fatty materials, such as edible fats and oils.

, For a number of years there have been on the market certain monoand di-esters of higher fatty acids and glycerine. Among such compounds were distearate and monostearate of glycerine, and monoesters of glycerine and saturated and unsaturated fatty acids. Such materials had been incorporated in edible oils and fats in minor proportions, such as the hydrogenated shortenings, lard or synthetic compositions of this general'type in order to improve the properties of such .shortenings for various culinary uses. All of the compounds so added had free or unesterified hydroxy groups on the glyceryl radical together with relatively long carbon chain of the acid component so that the compounds were relatively soluble in the fat, but at the same time they had hydrophilic groups, namely, OH groups, which would impart to the shortening emulsifying properties.

Toa certain extent the desired results were accomplished by such compounds but it was found that when a shortening of this type was used for frying purposes, it had a great tendency to smoke at relatively low temperatures, which rendered it quite objectionable for the purpose. Also, in order to obtain adequate emulsifying effects, it was necessary to add relatively large quantities thereof to the shortening or the like; In so-called high ratio products wherein more sugar than flour is used, such a shortening has found a considerable market, but it required relatively large amounts of the monoand diglycerides therein to obtain the desired result.v

It was necessary to add 5% or more of such compound in order to obtain good results as a high ratio shortening.

shortening, which does not depend on free hy-- droxy groups for providing adequate improved properties to the shortening, and which is eminently suitable for the purpose. I

It is also among the objects of the present invention to provide a composition containing such a constituent which is capable of use in the culinary arts for all purposes, including baking, frying, and in high ratio shortenings.

It is further among the objects of the present iii) invention to provide ajcomposition for introduction into vegetable and animal oils and fats which will provide an effectiveness far greater than that of the free hydroxyl containing emulsifiers previously used.

It is still further among the objects of the present invention to provide a highly efiicient agent in a shortening composition, whether liquid or solid, which will permit the sameto be used for,

frying purposes without emitting any'substantial amount of smoke at relatively high operating temperatures.

In practicing the present invention there is provided a series of esters of a polyethylene glycol having a molecular weight of at least 300; Better results are obtained with the higher molecular weight polyethylene glycols such as those having from 1000 to 2000 molecular weight and even higher, up to 4000. "In general, the molec-' ular weight of the polyethylene glycol is such that there are from 5 to ethylene glycol radicals in the molecule. v

Such a glycol is esterified witha fatty acid having at least 12 carbon atoms and up to the highest fatty acid found in vegetable and animal oils. Usually the amount of such fatty acid used in the reaction is sufficient to form the mono' The other hydroxy group ester of the glycol. of the glycol is esterified with a lower fatty acid having from 2 to 4 carbon atoms, namely, acetic, propionic and butyric acids and their isomers,

so that the final products are subtantially free from unesterified 0H radicals.

In some cases, the higher fatty acid, which may be saturated or unsaturated or may be a miX- ture of such fatty acids, is reacted in such quantities with the glycol that a di-ester is formed. This has substantial value as an'improving agent in shortenings. V

The following are specificexamples of the operation of the present invention.

Example 1 The starting material is polyethylene glycol having an approximate molecular weight of 1370, consisting of approximately 31 ethylene glycol radicals. 685 grams, equal to M; mol. of the glycol, is mixed with grams of commercial stearic acid obtained from hydrogenatedsoya bean oil and having an iodine number of 2, being about mol. l

The mixture is placed in a closed vessel' connected to a vacuum pump and it is heated gradually to a temperature of 225 C. with continuous agitation and with the introduction of a flow of nitrogen to act as a blanket in the vessel,

The vacuum is increased during the heating cycle so that when the temperature has reached 225 C. in about six hours, the pressure is from 5 to millimeters mercury absolute. At such temperature, heating is continued and the vacuum is maintained until the percentage of free fatty acid has dropped below 4. Water is removed continuously during the operation and upon com-.- pletion of the reaction, the product is allowed to cool to about 135 C.

Thereupon there is added to the reaction product, which is substantially the'pojlyglycol monostearate, 60 grams of acetic anhydride (98%), equivalent to slightly over 1.'2;mo l s. Heating is resumed and continued until the temperature has reached 200 to 210 C. A reflux condenser is provided so as to condense theivaporized acetic anhydride, which is returned for further reac-' tion. The refluxing is continued for about one hour, or until substantially complete ester'i'fica tion with the acetieanhydride has taken place.

The: resulting product is then usuallyftreate'd to remove any residual acetic an-nyenee and afcetic acid presentfby means of steam or by application of vacuum at elevated temperature. The resultingproductmay be filtered to remove suspended matter and cooled to room temperature. The diester so'forme'd is a waxy solid, soluble invegetable' and animaljoils and fats" and has llq grams of oleic acid.equivalent to moL, are placed in a suitable reaction vessel. About /2.% o zs dium hyd oxide 1 1. ue us 50 on is adde to th leic'a i waste a catalyst in the reaction, 7 The oleic acid is heated to 16 Q" n ethyle e o e is bu into. the reacticn vessel under the surface of the liquid, prefe ab y.. i cont nu s rrin u w o yl qu m or es ure .Tllfi ra e oiadd ti n is such that the ethylene oxide is. fuliyabsorbed. T i sc inu d n ab t .5.5 ams c et ene o de ha b ennt oduced. -Ihe eact ons Wh ht e p ace. include the fo mat on of. ac ym i ed thvl s y ol. endat th mini the op.- eration. .t ly thyleneely ol formed has a molecular ,Wi ht, -Of about 600 and is equivalent to mold At thesame time'under the tempera tur condition. the. mon leate of the pol ethylene glycol hasbeen -formed. v There isthjenadded to the product about .80 grams of propionicanhydride andesterification is caused, to take .place similarly to the second steppf Example -1. The resultingproduct may be steam refined and filtered, giving .thegpropionic-oleic 'ester of polyethylene glycol .600. p.

The products of Examples 1 and .2 described above may be added to a hydrogenated cottone seed shortening .in small amountsas from .;05'% to 0.2% with solution .ofythe idi-ester .infthe triglyceride. In such quantities the resulting shortening has a high degree of c're'aming quality and has been found suitable for generalculinary purposes. .In cake making; it imparts fluffines's to the baked prothict and the cake remains fresh for a longer period of time. In frying, as for instance in the making of potato chips, it has proven to have a 'high smoke point' so that rapid frying of various foods is obtained in a sat-is factory manner at a relatively hightemperature without the formation of smoke or discomfort to the operator. In high ratio shortenings from 012% to 1.0% of the di-esters added tdtlife fat is sufii'cient to provide a shortening which can be used in making high ratio baked products. Additional quantities of the di-esters may be introduced and up to 3 thereof has given excellent results. If desired, an amount up to 5.0% may be used but generally this has been found to be unnecessary. It has been found that l of many of the di-esters of the present invention are the equivalent of about 5% of glycerol monostearate previously used in high ratio shortening.

The present di-esters may be mixed with vegetable oils or animal oils as well as with the solid fats and the resulting products have similar properties fer fryingt cooking and baking purposes. Thel products are non-toxic and have a good flavor spatter, In the claims the term edible fat is intended to include the liquid as well as the solid fats.

Although the invention has been described setting ifo rth several specific embodiments thereof, the invention is not to be limited to the specific examples as they were given for. the purpose of illustrating the invention and not limiting git. Various changes in the details of the invention may be made within the spirit thereof. .For ii'nstance, the temperature, pressure and other eon: ditions of the operation may, be considerably varied in accordance with usual practice in order to give the desired esterification results The proportions, of the polygly'col vand the various fatty acids used may vary substantially fromthe exactiamounts herein s I ,JItIis not necessary that there be exactly on g'her fatty .acidankl one lowerfatty acid in each mole 1e buta m1; ation wherein there'is slightly more than one molecule on thelaverage of the 'higheno'r, lower fatty acid, still gives goodresults. Whileoutsid limits of proportions of the di-esters in oilsnand fats has been given, oneiumay vary from. these proportions to some slight extentbutsuch vari-F ation does not give any materially better effects. Mixtures of the dijesters of the present invention with the emulsifying .agents of the prior artrnay be incorporated .in shortenings" and the like.

These and other changes may be made within the principles herein ,setforth and the invention is to be broadly construed except as limited by the claims appended hereto.

Iclaim: i I

composition of matter consisting essentially of an edible fat having incorporated there: in from 0.05 to 5.0%,of acompcund takenfrom the class consisting of polyethylene glycol esters having the. following general formula:

RTOCI-Iz'CH) I'OR' wherein R .is a fatty acidxrad'ical' having at least 12 carbon atoms,i.R" is a fatty acid radical having 2 to .4 carbon atoms, and a is a whole nunfber from 5 to "60.

2. A composition of matter consisting essentially of an wedible-fat havi n'g incorporated therein from 0.05 to "5.0 :of a compound t'ak'en from the class consisting of having'th'e following general formula .-R(OCH2CH2).OR wherein His a satur'a'tedffatty acidiradiea'l having at least 12 carbon atoms,[R' is a fatty acid radical having 2 to 4 carbon atoms, and m is a vfhblenum ber from 5 to 60., r V v v I a. A composition of matter consisting essentially of'an edible fat havingjincorpora'ted"therein from 0.05%}9 513% of a compound taken from the class consisting I of polyethylene glycol esters having the following general formula:

polyethylene glycol esters" R (OCHzCI-Iz) zOR' wherein R is an unsaturated fatty acid radical having at least 12 carbon atoms, R is a fatty acid radical having 2 to 4 carbon atoms, and a; is a 7 whole number from to 60..

4. A composition of matter consisting essentially of an edible fat having incorporated therein from 0.05% to 5.0% of a compound taken from the class consisting of polyethylene glycol esters having the following general formula:

wherein R is a fatty acid radical having at least 12 carbon atoms, and :x: is a whole number from 5 to 60.

5. A composition of matter consisting essentially of an edible fat having incorporated therein from 0.05% to 5.0% of a compound taken from the class consisting of polyethylene glycol esters having the following general formula:

wherein R is a saturated fatty acid radical having at least 12 carbon atoms, and a: is a whole number from 5 to 60. I

6. A composition of matter consisting essentially of an edible fat having incorporated therein from 0.05% to 5.0% of a compound taken from the class consisting of polyethylene glycol esters having the following general formula:

CrzHss-COO (CHzCI-Iz-O) COCH3 wherein a; is a whole number from 5 to 60.

7 A composition of matter consisting essentially of'an edible fat having incorporated therein from 0.05% to 5.0% of a compound taken from the class consisting of polyethylene glycol esters having the following general formula:

mocnzcnmon' having the following general formula:

wherein R is a fatty acid radical having at least 12 carbon atoms, R is a fatty acid radical having 2 to 4 carbon atoms, wherein (OCH2CH2)a: has a molecular weight of 1000 to 2000.

EMERY I. VALKO.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,223,558 Epstein Dec. 3, 1940 2,303,432 Brown Dec. 1, 1942 2,306,315 Lycan Dec. 22, 1942 2,469,446 Strauss May 10, 1949 

7. A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF AN EDIBLE FAT HAVING INCORPORATED THEREIN FROM 0.05% TO 5.0% OF A COMPOUND TAKEN FROM THE CLASS CONSISTING OF POLYETHYLENE GLYCOL ESTERS HAVING THE FOLLOWING GENERAL FORMULA: 